Hydrophilic medical devices

ABSTRACT

A medical device including a plasma-treated porous substrate that is functionalized to provide a hydrophilic surface, and a process for preparing such a medical device, are disclosed. The method includes plasma treating at least a portion of a surface of a porous substrate with a gas species selected from oxygen, nitrogen, argon, and combination thereof. The gas species is configured to functionalize the surface of the medical device and form a hydrophilic surface.

TECHNICAL FIELD

The present disclosure relates to medical devices, and moreparticularly, to surgical implants having a hydrophilic surfacetreatment for improved wettability and cellular attachment.

BACKGROUND

The use of medical devices, and more specifically, implants, is known.However, the implants, once placed in situ, may dislocate or migrateand, thus, are frequently secured to tissue during surgery usingsurgical tacking devices or fasteners, such as staples, clips, tacks,sutures, and the like. Porous implants are often utilized for theirability to provide biologic fixation and integration into surroundingtissue. The increased surface area of the implant allows for tissueinfiltration into the implant via pores. The rate of tissue ingrowth islimited, however, and influenced by factors such as the porosity of theimplant, depth of the porosity, and length of time of implantation.

It would be advantageous to provide an implant with improved fluidabsorption and interaction with cells and biologic molecules. Such animplant would improve surgical site visibility during surgery by wickingaway excess fluid, improve pooling of coagulation and growth factorsnear a wound site, and improve favorable host tissue interactionsleading to infiltration and attachment of cell types important to woundhealing.

SUMMARY

In accordance with aspects of the present disclosure, a method of makingan absorbent surgical buttress, comprising: generating a plurality offibers; collecting the plurality of fibers so that they adhere to oneanother and form a non-woven material; plasma treating at least aportion of a surface of the non-woven material with an ionizable gasspecies or combination of ionizable gas species configured to chemicallymodify or functionalize the surface of the non-woven material; andcutting the non-woven material into a desired shape for a surgicalbuttress.

The method can include ionizable gas speciess selected from the groupconsisting of air, water vapor, oxygen, nitrogen, argon, andcombinations thereof. In certain embodiments, the fibers are meltextruded. The method of making the buttress can include blowing hot airat the fibers as they exit a die head and before they are collected. Thehot air blown at the fibers can have a temperature greater than or equalto the melting temperature of the fibers. In certain embodiments, thefibers are collected as they cool.

In certain embodiments, the fibers are melt extruded from a polymerselected from the group consisting of lactide homopolymer, glycolidehomopolymer, polydioxanone homopolymer, glycolide trimethylene carbonatecopolymer, glycolide lactide copolymer, glycolide dioxanone trimethylenecarbonate copolymer, and glycolide caprolactone trimethylene carbonatelactide copolymer.

In certain embodiments, the fibers are made from a bioabsorbablepolymeric material. The melting temperature of the polymer may bebetween about 180 and about 250 degrees celcius. In other embodiments,the melting temperature of the polymer is between about 80 degreescelcius and about 190 degrees celcius.

The hot air can have a temperature of between about 270 and about 290degrees celcius.

In certain embodiments, the fibers are collected on a conveyor surface.The method can include applying heat and pressure to the non-wovenmaterial before plasma treating the non-woven material.

In certain embodiments, the non-woven material is cut into a shapecorresponding to the shape of a linear surgical stapler. In otherembodiments, the non-woven material is cut into a shape corresponding tothe shape of a circular surgical stapler.

The fibers can be generated by melt extruding a copolymer of glycolide,caprolactone, trimethylene carbonate and lactide having a meltingtemperature between about 140 degrees celcius and about 185 degreescelcius. The hot air blown at the fibers can have a temperature betweenabout 185 degrees celcius and about 195 degrees celcius.

In certain embodiments, the fibers are generated by melt extrudingdioxanone having a melting temperature between about 80 degrees celciusand about 125 degrees celcius. The air blown at the dioxanone fibers canhave a temperature between about 145 degrees celcius and about 155degrees celcius.

In a further aspect of the present disclosure, an absorbent surgicalbuttress comprises a non-woven material having a plurality of fibersadhered to one another, the fibers being formed from a melt extrudedbioabsorbable polymeric material, the non-woven material being plasmatreated on at least a portion of a surface of the non-woven material sothat the surface is chemically modified or functionalized, the non-wovenmaterial being cut into a desired shape for the surgical buttress.

In certain embodiments, the fibers are formed from a polymeric materialselected from the group consisting of lactide homopolymer, glycolidehomopolymer, polydioxanone homopolymer, glycolide trimethylene carbonatecopolymer, glycolide lactide copolymer, glycolide dioxanone trimethylenecarbonate, and glycolide caprolactone trimethylene carbonate lactide.

The fibers may be formed from a polymeric material having a meltingtemperature of between about 180 and 250 degrees celcius. In certainembodiments, the fibers are formed from a polymeric material having amelting temperature of between about 80 degrees celcius and about 190degrees celcius

In certain embodiments, the non-woven material is cut into a shapecorresponding to the shape of a linear surgical stapler. In otherembodiments, the non-woven material is cut into a shape corresponding tothe shape of a circular surgical stapler.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing objects and advantages of the disclosure will become moreapparent from the reading of the following description in connectionwith the accompanying drawings, in which:

FIG. 1 is a perspective view of a surgical buttress in accordance withan embodiment of the present disclosure;

FIG. 2 is a schematic illustration of an apparatus which is suitable forcarrying out plasma treatment of a substrate in accordance with thepresent disclosure;

FIGS. 3A-3C are cross-sectional views of the surgical buttress of FIG.1, possessing filler materials in accordance with embodiments of thepresent disclosure;

FIG. 4 is a graph illustrating a comparison of liquid absorbance ofuntreated surgical buttresses and plasma treated surgical buttressesformed in accordance with an embodiment of the present disclosure; and

FIG. 5 is a graph illustrating a comparison of the rate of wicking ofthe plasma treated surgical buttresses of FIG. 4.

DETAILED DESCRIPTION

The present disclosure is directed to medical devices that have beenchemically modified to render at least a surface of a substrate of themedical device more hydrophilic than its native state. In the case ofporous devices, this surface treatment may enable the device to morequickly absorb and/or wick fluids, such as blood, interstitial fluid,cerebral spinal fluid, exudates, etc.

The following discussion includes a description of the presentlydisclosed medical device and an exemplary corresponding method oftreating the same in accordance with the principles of the presentdisclosure. For the purposes of discussion, the medical device will bediscussed in terms of a surgical buttress. However, those skilled in theart will appreciate the presently disclosed medical devices may be anysurgical implant, such as meshes, scaffolds, grafts (e.g., fabricsand/or tubes), rings, sutures, patches, slings, pledgets, growthmatrices, drug delivery devices, wound plugs, and, in general, softtissue repair devices and surgical prostheses. In other embodiments,suitable medical devices may be topically applied medical products, suchas wound dressings, coverings, gauzes, and the like, that can be used inmedical/surgical procedures.

Referring now to the figures, wherein like components are designated bylike reference numerals throughout the several views, FIG. 1 illustratesa surgical buttress 10, an example of a medical device in accordancewith the present disclosure, including a porous substrate 12. Poroussubstrate 12 includes openings 14, such as pores, voids, or holes overat least a portion of a surface thereof. The openings of the buttress ofthe present disclosure may be sized to permit fibroblast through-growthand ordered collagen laydown, resulting in integration of the buttressinto the body.

The openings may be present as a surface characteristic or a bulkmaterial property, which partially or completely penetrates thesubstrate, and may be uniformly or randomly distributed across portionsthereof. The buttress may have an open-cell structure, where theopenings are connected to each other, forming an interconnected network.In such embodiments, the openings may be in sufficient number and sizeso as to interconnect across the entire thickness of the substrate. Insome embodiments, the openings do not extend across the entire thicknessof the porous substrate, but rather are present at a portion of thesurface thereof. Conversely, the buttress may be closed cell, where theopenings are not interconnected. Those skilled in the art reading thepresent disclosure may envision other distribution patterns andconfigurations of the openings in the porous substrate. It is envisionedthat the substrate may, in embodiments, be partially or fullynon-porous.

In embodiments, suitable materials for the porous substrate include, butare not limited to foams (e.g., open or closed cell foams). Where theporous substrate is a foam, the substrate may be formed using any methodsuitable to forming a foam or sponge including, but not limited to,lyophilization or freeze-drying of a composition. Suitable techniquesfor making foams are within the purview of those skilled in the art.

In embodiments, openings may be formed in filamentous buttresses via thespaces formed between the filaments of the buttress. Alternatively, thebuttress may be formed from a continuous yarn that is arranged in loopsthat give rise to the openings in the buttress. The size of the openingsbetween the filaments and spacing therebetween may vary depending on thesurgical application and desired implant characteristics as envisionedby those skilled in the art.

The filaments may be made using any technique within the purview ofthose skilled in the art, such as, for example, extrusion, molding,and/or gel spinning. In embodiments, the filaments may be extrudedthrough an extruder unit of a conventional type, such as those disclosedin U.S. Pat. Nos. 6,063,105, 6,203,564, and 6,235,869, the entiredisclosures of each of which are incorporated by reference herein. Inembodiments, filaments may be subsequently brought together into a groupto form a yarn.

Once formed, a plurality of the filaments may then be braided, twisted,aligned, fused, entangled, intertwined, or otherwise joined or arrangedto form a variety of different buttress shapes and sizes. Inembodiments, the filaments may be drawn, oriented, crinkled, twisted,braided, commingled, or air entangled to form the buttress. Thefilaments may be woven, knitted, interlaced, braided, or formed into abuttress by non-woven techniques. The structure of the buttress willvary depending upon the assembling technique utilized to form thedevice, as well as other factors, such as the type of fibers used, thetension at which the fibers are held, and the mechanical propertiesrequired of the buttress.

In embodiments, knitting may be utilized to form a buttress of thepresent disclosure. Knitting involves, in embodiments, the intermeshingof filaments, or yarns thereof, to form loops or inter-looping of thefilaments. In some embodiments, filaments may be warp-knitted therebycreating vertical interlocking loop chains and/or may be weft-knittedthereby creating rows of interlocking loop stitches across the buttress.In other embodiments, weaving may be utilized to form a buttress of thepresent disclosure. Weaving may include, in embodiments, theintersection of two sets of straight filaments, or yarns thereof, warpand weft, which cross and interweave at right angles to each other, orthe interlacing of two filaments at right angles to each other. In someembodiments, the filaments may be arranged to form a net mesh which hasisotropic or near isotropic tensile strength and elasticity.

In an embodiment, a nonwoven material is formed from lactidehomopolymer, glyciolide homopolymer, polydioxanone homopolymer,glycolide lactide copolymer, glycolide dioxanone trimethylene carbonatecopolymer, glycolide caprolactone trimethylene carbonate lactidecopolymer, or glycolide trimethylene carbonate copolymer. The polymerresin is melt extruded and the melt pump meters molten polymer into adie head. The melt pump speed is between about 2 and about 12 rpm. Thepolymer is forced through the array of holes in the die head, which hasholes from about 0.13 mm diameter to about 0.3 mm diameter, in someembodiments, from about 0.175 mm diameter to about 0.25 mm diameter. Thetemperature at the die head is between about 200 degrees celsius andabout 275 degrees celsius in some embodiments, from about 235 degreescelsius and about 255 degrees Celsius in some embodiments, and thepressure at the head is between about 10 bar and about 80 bar. Thepolymer fibers exiting the die are forced onto a conveyor belt byblowing hot air. The hot air has a temperature of between about 230degrees celsius and about 325 degrees celsius in some embodiments, andfrom about 265 degrees celsius and about 295 degrees Celsius in someembodiments. The speed of the conveyor belt is between about 1 meter perminute and about 10 meters per minute. The fibers randomly land on theconveyor belt and build up to several layers in thickness. Suction isapplied through the conveyor belt surface to help compact the fibersagainst each other as they cool. The material may be introduced intocalendaring rolls to apply heat and pressure prior to being collectedand staged. The material is then annealed to drive out any monomer andadvance the crystallization of the polymer. Desirably, the material hasa porosity of between about 50% and about 90%. The fiber diameters isbetween about 5 μm and about 100 μm. The material thickness is betweenabout 150 μm and about 400 μm.

It is contemplated that the fibers can be generated at lowertemperatures. In certain embodiments, fibers are formed from a polymerhaving a lower melting temperature. For example, a copolymer ofglycolide, caprolactone, trimethylene carbonate and lactide could bemelt extruded at between about 140 degrees celcius and about 185 degreescelcius. The hot air blown at the fibers has a temperature between about185 degrees celcius and about 195 degrees celcius. In another example,dioxanone is melt extruded at between about 80 degrees celcius and about125 degrees celcius. The hot air blown at the dioxanone fibers has atemperature between about 145 degrees celcius and about 155 degreescelcius. Thus, the buttress may formed from fibers melt extruded frompolymers having a melting temperature of between about 80 degreescelcius and about 190 degrees celcius.

In embodiments, the filaments may be nonwoven and formed bymechanically, chemically, or thermally bonding the filaments, or yarnsthereof, into a sheet or web in a random or systematic arrangement. Forexample, filaments may be mechanically bound by entangling the filamentsto form the buttress by means other than knitting or weaving, such asmatting, pressing, stitch-bonding, needlepunching, or otherwiseinterlocking the filaments to form a binderless network. In otherembodiments, the filaments of the buttress may be chemically bound byuse of an adhesive such as a hot melt adhesive, or thermally bound byapplying a binder such as a powder, paste, or melt, and melting thebinder on the sheet or web of filaments. In embodiments, the buttressmay be spunbound and/or meltblown.

The diameter of the individual filaments may be from about 5 μm to about100 μm, in embodiments, from about 10 μm to about 40 μm in someembodiments, and from about 15 μm to about 35 μm in some embodiments,and in some further embodiments, from about 18 μm to about 33 μm. Thefinished fabric thickness may be from about 150 μm to about 400 μm inembodiments, and from about 150 μm to about 300 μm in some embodiments,and from about 200 μm to about 250 microns in some embodiments, and insome further embodiments about 230 μm. The finished fabric weight may befrom about 75 g/m² to about 100 g/m², in embodiments, from about 80 g/m²to about 95 g/m², and in some embodiments, about 87 g/m². It should beunderstood that different fabric thicknesses, weights, and porositiesmay be selected by varying manufacturing conditions.

The porous substrate may include any biocompatible natural or syntheticmaterial. The material may be bioabsorbable or non-bioabsorbable. Itshould of course be understood that any combination of natural,synthetic, bioabsorbable and non-bioabsorbable materials may be used toform the porous substrate.

Suitable synthetic biodegradable materials include polymers such asthose made from lactide, glycolide, caprolactone, valerolactone,carbonates (e.g., trimethylene carbonate, tetramethylene carbonate, andthe like), dioxanones (e.g., 1,4-dioxanone), δ-valerolactone,1,dioxepanones (e.g., 1,4-dioxepan-2-one and 1,5-dioxepan-2-one),ethylene glycol, ethylene oxide, esteramides, γ-hydroxyvalerate,β-hydroxypropionate, alpha-hydroxy acid, hydroxybuterates, poly (orthoesters), hydroxy alkanoates, tyrosine carbonates, poly(imidecarbonates), poly(imino carbonates) such as poly (bisphenolA-iminocarbonate) and poly (hydroquinone-iminocarbonate), polyurethanes,polyanhydrides, polymer drugs (e.g., polydiflunisol, polyaspirin, andprotein therapeutics), and copolymers and combinations thereof.

In embodiments, the porous substrate may be fabricated from a lactomercopolymer of glycolide and lactide derived from glycolic and lacticacids. In embodiments, the porous substrate may be fabricated frompolyglyconate, a copolymer of glycolic acid and trimethylene carbonate.

In other embodiments, the porous substrate may be fabricated from asynthetic polyester composed of glycolide, dioxanone, and trimethylenecarbonate. The polymer may include from about from about 50% to about70% by weight glycolide, in embodiments, from about 55% to about 65% byweight glycolide, and in some embodiments, about 60% by weightglycolide; from about 4% to about 24% by weight dioxanone, inembodiments, from about 9% to about 19% by weight dioxanone, and in someembodiments, about 14% by weight dioxanone; and from about 16% to about36% by weight trimethyl carbonate, in embodiments, from about 21% toabout 31% by weight trimethyl carbonate, and in some embodiments, about26% by weight trimethyl carbonate.

In yet other embodiments, the porous substrate may be fabricated from acopolymer of glycolide and trimethylene carbonate. The polymer mayinclude from about 55% to about 75% by weight glycolide, in embodiments,about 60% to about 70% by weight glycolide, and in some embodiments,about 65% by weight glycolide, and from about 25% to about 45% by weighttrimethylene carbonate, in embodiments, from about 30% to about 40% byweight trimethylene carbonate, and in some embodiments, about 35% byweight trimethylene carbonate.

In accordance with the present disclosure, the filaments and/orbuttresses formed therefrom are chemically modified to render at least aportion of a surface of the filaments and/or buttress hydrophilic. Thetreatment process may render all, or most, surfaces of the substratehydrophilic, including the surfaces of the openings or pores. Inembodiments, about 25% to about 99% of the surfaces of the substrate arerendered hydrophilic, in some embodiments, about 40% to about 95% of thesurfaces, and in some further embodiments, about 60% to about 90% of thesurfaces. The treatment process does not require a secondary material tobe coated or bound to the porous substrate to impart hydrophilicity,although in alternate embodiments, the chemical modification may resultfrom the deposition of a coating material on the surface to render itmore hydrophilic.

The chemical modification of the surface of the porous substrate may beby coronal discharge, low pressure plasma treatment, atmospheric plasmatreatment, or other plasma technology systems. The treatment processfunctionalizes the surface of the substrate to render the surface morehydrophilic.

For example, in embodiments, a plasma treatment is used. The plasma maybe formed of a single gas species such as oxygen, carbon dioxide,ammonia, nitrogen, or argon. The use of oxygen, for example, will resultin surface activation of an oxygenate type, such as the formation of—OH, —CHO, and/or —COOH groups. It is envisioned that other gases,mixtures of gases, vapours of volatile organic molecules such asalcohols, water, or open air plasma may also be utilized. For example,ozone may be used in place of oxygen. In other examples, the plasma gasmay be produced using an oxygen-containing molecule, anitrogen-containing molecule, or mixtures thereof. In some embodiments,plasma gases may be used serially.

The surface of the substrate is modified with the addition of oxygen,other charged species, and/or hydrophilic moieties that will increasehydrostatic interactions both with water molecules and with hydrophilicdomains of biologic molecules, such as proteins. In turn, undesirablehydrophobic interactions, such as protein hydrophobic domain bonding andloss of protein native structure, will be reduced at the substrate'ssurface, potentially minimizing adverse host inflammatory response.

An illustrative plasma treatment apparatus is shown in FIG. 2. Plasmatreatment apparatus 20 includes a chamber 21 including a rack 22, suchas a stainless steel rack, and a pair of parallel electrode plates 24and 26 between which a plasma is formed. A radio frequency generator 23is provided as a source of potential, with an output terminal of thegenerator 23 being connected to electrode plate 24 and electrode plate26 being grounded, thereby providing means for generating an electricalfield between the electrode plates 24 and 26, in which field the plasmacan be created and sustained. To provide the desired gas from which theplasma is formed, the apparatus 20 includes a plasma gas source 30(typically a standard gas cylinder) connected through a gas inlet system32 to the chamber 21. The plasma gas source 30 includes a valve 36 forcontrolling the flow of gas through a supply line 34. A purge gas source42, such as helium, is also connected through a line 44 and valve 38 togas inlet system 32. A vacuum pump 40 is connected to the chamber 21 forreducing the gas pressure therein.

In a typical reaction, the porous substrate (for example, as depicted inFIG. 1) is mounted within the chamber 21 on the rack 22, positionedbetween electrode plates 24 and 26. Alternatively, the rack 22 may bemovable so that the porous substrate may be pulled through the chamber21. Alternatively, the porous substrate may travel through the plasmafield between reels in a continuous reel to reel system requiring nosupport rack. The vacuum pump 40 is operated to reduce the pressure inthe chamber 21. The gas inlet system 32 is operated to permit reactinggas monomer from plasma gas source 30 to flow into the chamber 21through the supply line 34 before generating a plasma.

The plasma is created by applying the output of the radio frequencygenerator 23 to the electrode plate 24. The power supplied by thegenerator 23 is at the minimum required to sustain the plasma, as higherpowered plasma will only degrade the surface of the substrate. Thereaction between the plasma and the substrate is allowed to proceed fora period of time determined by the desired thickness and surface energyon the substrate and the concentration of gas monomers in the reactingvapor. The pressure within the chamber 21 is measured by a capacitancemanometer 46 to maintain appropriate pressure throughout the reactionperiod.

Following the reaction period, the flow of gas from the plasma gassource 30 is terminated, the power from the generator 23 sustaining theplasma is turned off, and valve 38 is Opened to permit gas to flow intothe chamber 21 from purge gas source 42 to purge the substrate surfaceof highly reactive radicals which could cause premature contamination ofthe substrate's surface. Valve 38 is then closed, the chamber 21 isopened so that chamber 21 is returned to atmospheric pressure, and theplasma treated substrate is removed.

The plasma treated substrate may then be sterilized by any means withinthe purview of those skilled in the art including, but not limited to,ethylene oxide, electron beam, gamma irradiation, autoclaving, plasmasterilization, and the like.

It should be understood that the conditions under which treatment occursmay be dependent upon a number of factors, such as the type, size,thickness, and porosity of material being treated, the type andconcentration of gas species being utilized and the flow rate thereof,the plasma technology system being utilized, and plasma treatmentconditions such as voltage, pressure, temperature, duration, and thelike.

For example, the plasma may include from about 1% to about 100% byweight of oxygen, nitrogen, or argon, in embodiments, from about 15% toabout 90% by weight of oxygen, nitrogen, or argon, and in someembodiments, from about 25% to about 75% by weight oxygen, nitrogen, orargon. The gas may have a mass flow rate of from about 10 sccm to about200 seem, in embodiments, from about 25 seem to about 150 sccm, and insome embodiments, about 50 sccm to about 100 sccm. The plasma generatingelectrodes may operate at a power of about 25 watts to about 1000 watts,in embodiments, from about 50 watts to about 750 watts, and in someembodiments, about 100 watts to about 500 watts. The treatment pressuremay be about 25 mtorr to about 500 mtorr, in embodiments, from about 50mtorr to about 400 mtorr, and in some embodiments, from about 100 mtorrto about 250 mtorr. The treatment may occur at a temperature of lessthan 100° C., and, in embodiments, at ambient temperature. The length ofexposure may range from about 10 seconds to about 120 minutes, inembodiments, from about 30 seconds to about 60 minutes, and in someembodiments, from about 2 minutes to about 30 minutes. It will beappreciated by those skilled in the art that the treatment conditionsmay be outside the ranges set forth as discussed above.

In embodiments, the substrate treated in accordance with the presentdisclosure may also be subjected to a plasma polymerization process toform a polymer coating on at least a portion of the surface of thesubstrate. Such methods are disclosed, for example, in U.S. Pat. No.7,294,357, the entire disclosure of which is incorporated herein by thisreference.

The monomers used to form the polymer coating may be polymerizeddirectly on the substrate's surface using plasma-state polymerizationtechniques generally known to those skilled in the art. In brief, themonomers are polymerized onto the surface of the substrate by activatingthe monomer in a plasma state. The plasma state generates highlyreactive species, which form a highly cross-linked and highly-branchedultra-thin polymer coating, which is deposited on the surface of thesubstrate during plasma polymerization.

In embodiments, a suitable organic monomer or a mixture of monomershaving polymerizable unsaturated groups is introduced into the chamberwhere it is fragmented and/or activated forming further excited speciesin addition to the activated plasma gases. The excited species andfragments of the monomer recombine upon contact with the substrate'ssurface to form a largely undefined structure which contains a complexvariety of different groups and chemical bonds and forms a highlycross-linked polymer coating on the surface of the substrate. If oxygen,nitrogen, argon, or molecules possessing these elements are present,either within the plasma reactor during the polymer coating process oron exposure of the polymer coated substrate to oxygen or air subsequentto the plasma process, the polymeric deposit will include a variety ofpolar groups.

In embodiments, plasma polymerization may utilize solvents such asdiglyme and tetraglyme, to produced PEG-like surfaces. In otherembodiments, plasma polymerization may utilize fluorochemicals such asaliphatic fluorine-containing gases, to produced fluorinated polymersurfaces.

The amount and relative position of polymer deposition on the substratesare influenced by at least three geometric factors: (1) location of theelectrode plates and distribution of charge; (2) monomer flow; and (3)substrate position within the chamber. In practice, an electricdischarge from the RF generator may be applied to the electrode plateswithin the chamber and the selected monomers may be introduced into thechamber and energized into a plasma, saturating the space between theelectrode plates with an abundance of energetic free radicals and lesseramounts of ions and free electrons produced by the monomers. As thesubstrate is passed through, or positioned between, the electrodeplates, the surface of the substrate is bombarded with free radicals,resulting in the formation of the polymer coating.

In embodiments, siloxane monomers with hydrophilic end groups may beused in the plasma polymerization process to produce polymer coatings onthe substrate's surface. In some embodiments, aliphatichydrocyclosiloxane monomers, alone or mixed with co-monomers, may beutilized to provide polymer coatings having a homogenous or mixedproperty coating. For example, by introducing reactive functionalizingmonomers, organo-based monomers, or fluorocarbon monomers together withthe aliphatic hydrocyclosiloxane monomers in the plasma polymerizationsystem, physical pore size and chemical affinity of the plasmacopolymerized aliphatic hydrocyclosiloxane coating with selectivemonomers can be controlled. This allows the use of the copolymerizedplasma polymer coating for applications which require the coating todifferentiate between certain types of gases, ions, and molecules and italso may be utilized to introduce functional groups to the polymercoating which, in turn, can help link hydrophilic molecules to thepolymer coating.

The openings in the substrate may be partially or completely filled withfiller material, such as uncrosslinked molecules, hydrogels, absorbablepolymer spheres, or interpenetrating chemically or ionically crosslinkedhydrogels. In embodiments, the filler material may fill about 5% toabout 100% of the openings in the substrate, in some embodiments, about10% to about 80% of the openings, and in some other embodiments, fromabout 25% to about 75% of the openings. The filler material may beincorporated into the buttress during fabrication, prior to plasmatreatment, and/or may be incorporated into the substrate after plasmatreatment.

The structure of the porous substrate provides the infrastructure forthe buttress or other medical device formed thereof and the fillermaterial may provide a reservoir for the delivery of drugs or otherfactors from the substrate and/or a repository of protein, cell, orgrowth factor recruiting moieties that encourage tissue healing or cellgrowth when the medical device is implanted within the body.

For example, hydrogels may be used as a means to absorb blood and ascarriers of thrombogenic agents for blood clotting and hemostasis atwound sites. Hydrogels can be modified with any number of conjugatedmolecules such as cell adhesion proteins, growth factors, peptides, andendogenous growth factor capturing molecules, such as heparin sulfate,to promote tissue ingrowth and healing. In embodiments, the fillermaterial may include releasable factors that have an associated bindinginteraction that will release agents by unbinding and diffusion, orfiller material degradation.

Examples of filler materials which may be utilized in accordance withthe present disclosure for example, include: anti-adhesives;antimicrobials; analgesics; antipyretics; anesthetics; antiepileptics;antihistamines; anti-inflammatories; cardiovascular drugs; diagnosticagents; sympathomimetics; cholinomimetics; antimuscarinics;antispasmodics; hormones; growth factors; muscle relaxants; adrenergicneuron blockers; antineoplastics; immunogenic agents;immunosuppressants; gastrointestinal drugs; diuretics; steroids; lipids;lipopolysaccharides; polysaccharides; platelet activating drugs;clotting factors; and enzymes. It is also intended that combinations offiller materials may be used.

Other filler materials include: local anesthetics; non-steroidalantifertility agents; parasympathomimetic agents; psychotherapeuticagents; tranquilizers; decongestants; sedative hypnotics; steroids;sulfonamides; sympathomimetic agents; vaccines; vitamins; antimalarials;anti-migraine agents; anti-parkinson agents such as L-dopa;anti-spasmodics; anticholinergic agents (e.g., oxybutynin);antitussives; bronchodilators; cardiovascular agents, such as coronaryvasodilators and nitroglycerin; alkaloids; analgesics; narcotics such ascodeine, dihydrocodeinone, meperidine, morphine and the like;non-narcotics, such as salicylates, aspirin, acetaminophen,d-propoxyphene and the like; opioid receptor antagonists, such asnaltrexone and naloxone; anti-cancer agents; anti-convulsants;anti-emetics; antihistamines; anti-inflammatory agents, such as hormonalagents, hydrocortisone, prednisolone, prednisone, non-hormonal agents,allopurinol, indomethacin, phenylbutazone and the like; prostaglandins;cytotoxic drugs; chemotherapeutics, estrogens; antibacterials;antibiotics; anti-fungals; anti-virals; anticoagulants; anticonvulsants;antidepressants; antihistamines; and immunological agents.

Examples of yet other suitable filler materials include: viruses andcells; peptides, polypeptides and proteins, as well as analogs, muteins,and active fragments thereof; immunoglobulins; antibodies; cytokines(e.g., lymphokines, monokines, chemokines); blood clotting factors;hemopoietic factors; interleukins (IL-2, IL-3, IL-4, IL-6); interferons(β-IFN, α-IFN and γ-IFN); erythropoietin; nucleases; tumor necrosisfactor; colony stimulating factors (e.g., GCSF, GM-CSF, MCSF); insulin;anti-tumor agents and tumor suppressors; blood proteins such as fibrin,thrombin, fibrinogen, synthetic thrombin, synthetic fibrin, syntheticfibrinogen; gonadotropins (e.g., FSH, LH, CG, etc.); hormones andhormone analogs (e.g., growth hormone); vaccines (e.g., tumoral,bacterial and viral antigens); somatostatin; antigens; blood coagulationfactors; growth factors (e.g., nerve growth factor, insulin-like growthfactor); bone morphogenic proteins; TGF-B; protein inhibitors; proteinantagonists; protein agonists; nucleic acids, such as antisensemolecules, DNA, RNA, RNAi; oligonucleotides; polynucleotides; andribozymes.

As illustrated in FIG. 3A, the filler material 50 a may benon-crosslinked molecules which are embedded within the openings 14 a ofthe substrate 12 a of the buttress 10 a by conventional methods withinthe purview of those skilled in the art, such as by solvent solutionimpregnation and subsequent solvent evaporation. Examples ofnon-crosslinked molecules which may be included with the above fillersinclude, for example, high molecular weight PEG, polyalkylene oxidessuch as PLURONICS, PEG-poly(alpha-hydroxy esters) block copolymers,poly(vinyl pyrrolidone), poly(vinyl alcohol), polyacrylates andpolyacrylate copolymers, such as poly(acrylic acid), poly(methacrylicacid), poly(sodium acrylate), poly(2-hydroxyethyl methacrylate), poly(potassium sulfopropyl acrylate) and their copolymers, dextran,alginate, carboxymethyl cellulose, chitosan, hyaluronic acid, fibrin,gelatin, collagen, laminin, oxidized cellulose, and combinationsthereof.

FIG. 3B illustrates a buttress 10 b including a plurality of fillermaterial 50 b in the form of beads. The beads 50 b may be incorporatedinto and/or onto at least a portion of the openings 14 b of thesubstrate 12 b in a systematic or random distribution pattern. Inembodiments, the filler material 50 b itself may be shaped and formedinto a bead 50 b. Alternatively, each bead may include a casing (notshown) made from a degradable polymeric material which defines a corecontaining a quantity of filler material 50 b therein. The beads 50 bmay be entrapped within the buttress 10 b so that they may be deliveredand held at the tissue site without appreciable bead migration. Inembodiments, the beads 50 b may be blown onto, or laid into, theopenings 14 b of the substrate 12 b during buttress fabrication asfilaments are being deposited on a target surface so that the beads 50 bare trapped between filaments as intrafiber bonds form. Beads 50 b maybe formed from hydrogels composed of PEG based polymers, dextran, pHEMA,carboxymethyl cellulose, or alginate, for example. Other materials forforming beads include, for example, polyalpha-hydroxy esters) configuredas single or multilayered beads. In some embodiments, charged dextranbeads may be incorporated into buttress 10 b. It is envisioned that avariety of beads may be incorporated into a buttress 10 b of the presentdisclosure.

FIG. 3C illustrates a buttress 10 e including an interpenetratingnetwork of filler material 50 c. In embodiments, the openings 14 c ofthe porous substrate 12 c is impregnated with hydrogel precursors whichare crosslinked to form the interpenetrating network 50 c throughout thebuttress 10 c. Hydrogel precursors include, for example, PEGpoly(alpha-hydroxy esters) block copolymers, hyaluronic acid, collagen,and alginate.

The following non-limiting example illustrates the improved wettabilityof substrates formed in accordance with the present disclosure.

EXAMPLES Example 1

A nonwoven material was formed from a glycolide trimethylene carbonatecopolymer, having a melting temperature of approximately 215 degreescelsius. The polymer resin was melt extruded at a temperature of betweenabout 180 and about 250 degrees celsius. A melt pump metered the Moltenpolymer into a die head. The polymer melt was forced through an array ofholes in the die head. Various die head types have hole configurationsranging from 0.13 to 0.25 min in diameter. The temperature at the diehead was about 240 degrees celsius at a head pressure of approximately30 bar, depending on die head type. The polymer fibers exiting the diewere forced onto a moving conveyor belt by means of compressed/blown hotair. The hot air had a temperature of between about 270 degrees celsiusand about 290 degrees celsius, which is hotter than the melt temperatureof the polymer. The conveyor belt speed was about 8 meters per minute.The fibers randomly landed on the conveyor belt and built up to severallayers in thickness. Suction was applied through the conveyor beltsurface to help compact the fibers against each other as they cooled.The material was then introduced into a calendaring roll device whichheated and compressed the fabric material i.e., enhancing the polymerstate of crystallization and thickness uniformity. The material was thencollected and stored. In a subsequent process the material was annealedat a temperature of about 120 celsius to remove residual monomers and toallow any crystallization potential of the polymer to complete.Individual fiber diameters ranged from 5 μm to 30 μm. The resultingmaterial has a porosity of about 50% to about 90%. The materialthickness was about 230 μm. The material was then plasma treated.

Example 2

A first set of nonwoven buttresses, set A, were formed from a copolymerof glycolic acid and trimethylene carbonate. A second set of nonwovenbuttresses, set B, were formed from a copolymer of glycolide (65%) andtrimethylene carbonate (35%). The fibers of each buttress definedinterconnected openings that extended throughout the buttress in atortuous path. One buttress from each set was left untreated while asecond buttress was plasma treated for 5 minutes at 500 Watts in asingle gas atomosphere.

An outer edge of each buttress was held in a pool of dyed albuminsolution used to simulate blood, to both observe and measure liquidabsorption by the buttresses. Results for each buttress are provided inFIG. 4. As shown in FIG. 4, the plasma treated buttresses providedgreater liquid absorbance. The rate of wicking of each of the plasmatreated buttresses is illustrated in FIG. 5.

The present disclosure also incorporates aspects described in thefollowing numbered paragraphs.

1. A method of making an absorbent surgical buttress, comprising:generating a plurality of fibers; collecting the plurality of fibers sothat they adhere to one another and form a non-woven material; plasmatreating at least a portion of a surface of the non-woven material withan ionizable gas species or combination of ionizable gas speciesconfigured to chemically modify or functionalize the surface of thenon-woven material; and cutting the non-woven material into a desiredshape for a surgical buttress.

2. The method of making an absorbent surgical buttress according toclaim 1, wherein the ionizable gas species is selected from the groupconsisting of air, water vapor, oxygen, nitrogen, argon, andcombinations thereof.

3. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 2, wherein the fibers are melt extruded.

4. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 3, further comprising blowing hot air at thefibers as they exit a die head and before they are collected.

5. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 though 4, further comprising blowing hot air at thefibers as they exit the die head and before they are collected, the hotair having a temperature greater than or equal to the meltingtemperature of the fibers.

6. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 though 5, wherein the fibers are collected as theycool.

7. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 6, wherein the fibers are melt extruded froma polymer selected from the group consisting of lactide homopolymer,glycolide homopolymer, polydioxanone homopolymer, glycolide trimethylenecarbonate copolymer, glycolide lactide copolymer, glycolide dioxanonetrimethylene carbonate copolymer, and glycolide caprolactonetrimethylene carbonate lactide copolymer.

8. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 7, wherein the fibers are made from abioabsorbable polymeric material.

9. The method of making an absorbent surgical buttress according to anyone of paragraph 1 through 8, wherein the melting temperature of thepolymer is between about 180 and about 250 degrees celcius.

10. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 9, wherein the melting temperature of thepolymer is between about 80 degrees celsius and about 190 degreescelcius.

11. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 10, wherein the hot air has a temperature ofbetween about 270 and about 290 degrees celcius.

12. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 11, wherein the fibers are collected on aconveyor surface.

13. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 12, further comprising applying heat andpressure to the non-woven material before plasma treating the non-wovenmaterial.

14. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 13, wherein the non-woven material is cutinto a shape corresponding to the shape of a linear surgical stapler.

15. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 14, wherein the non-woven material is cutinto a shape corresponding to the shape of a circular surgical stapler.

16. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 15, wherein the fibers are generated by meltextruding a copolymer of glycolide, caprolactone, trimethylene carbonateand lactide having a melting temperature between about 140 degreescelcius and about 185 degrees celcius.

17. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 16, wherein the hot air blown at the fibershas a temperature between about 185 degrees celcius and about 195degrees celcius.

18. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 17, wherein the fibers are generated by meltextruding dioxanone having a melting temperature between about 80degrees celcius and about 125 degrees celcius.

19. The method of making an absorbent surgical buttress according to anyone of paragraphs 1 through 18, wherein the air blown at the dioxanonefibers has a temperature between about 145 degrees celcius and about 155degrees celcius

20. An absorbent surgical buttress, comprising a non-woven materialhaving a plurality of fibers adhered to one another, the fibers beingformed from a melt extruded bioabsorbable polymeric material, thenon-woven material being plasma treated on at least a portion of asurface of the non-woven material so that the surface is chemicallymodified or functionalized, the non-woven material being cut into adesired shape for the surgical buttress.

21. The absorbent surgical buttress according to paragraph 20, whereinthe fibers are formed from a polymeric material selected from the groupconsisting of lactide homopolymer, glycolide homopolymer, polydioxanonehomopolymer, glycolide trimethylene carbonate copolymer, glyeolidelactide copolymer, glycolide dioxanone trimethylene carbonate, andglycolide caprolactone trimethylene carbonate lactide.

22. The absorbent surgical buttress according to any one of paragraphs20 through 21, wherein the fibers are formed from a polymeric materialhaving a melting temperature of between about 180 and 250 degreescelcius.

23. The absorbent surgical buttress according to any one of paragraphs20 through 22, wherein the fibers are formed from a polymeric materialhaving a melting temperature of between about 80 degrees celcius andabout 190 degrees celcius

24. The absorbent surgical buttress according to any one of paragraphs20 through 23, wherein the non-woven material is cut into a shapecorresponding to the shape of a linear surgical stapler.

25. The absorbent surgical buttress according to any one of paragraphs20 through 24, wherein the non-woven material is cut into a shapecorresponding to the shape of a circular surgical stapler.

26. A method of preparing a medical device having a hydrophilic surface,the method comprising: plasma treating at least a portion of a surfaceof a porous medical device with a gas species selected from the groupconsisting of oxygen, nitrogen, argon, and combinations thereof, the gasspecies being configured to functionalize the surface of the medicaldevice and form a hydrophilic surface.

27. The method of paragraph 26, wherein plasma treating comprises:placing the medical device within a chamber between a pair of electrodeplates; releasing the gas species into the chamber; and generating anelectrical field between the pair of electrode plates to sustain aplasma.

28. The method of paragraph 27, wherein plasma treating furthercomprises: terminating the flow of the gas species into the chamber; andpurging the surface of the medical device with an inert gas.

The method of any one of paragraphs 26 through 28, further comprisingsterilizing the plasma treated medical device.

The method of any one of paragraphs 26 through 29, further comprisingintroducing a filler material into openings of the medical device.

The method of any one of paragraphs 26 through 30, further comprisingcoating at least a portion of the surface of the medical device withmonomers including hydrophilic end groups.

32. The method of any one of paragraphs 26 through 31, furthercomprising polymerizing at least a portion of the surface of the medicaldevice with functionalizing monomers by introducing the monomers intothe chamber with the gas species.

33. A medical device comprising a plasma-treated porous substrate thatis functionalized to provide a hydrophilic surface, the porous substrateincluding a filler material embedded within at least a portion ofopenings therein.

34. The medical device of paragraph 33, wherein the substrate isselected from the group consisting of buttresses, meshes, scaffolds,grafts, rings, sutures, patches, slings, pledgets, growth matrices, drugdelivery devices, wound plugs, soft tissue repair devices, surgicalprostheses, wound dressings, coverings, and gauzes.

35. The medical device of any one of paragraph 33 and 34, wherein thesubstrate is fabricated from a synthetic biodegradable polymer.

36. The medical device of any one of paragraphs 33 through 35, whereinthe synthetic biodegradable polymer is selected from the groupconsisting of lactide, glycolide, caprolactone, trimethyl carbonate,dioxanone, and copolymers and combinations thereof.

37. The medical device of any one of paragraphs 33 through 36, whereinthe substrate is fibrous and includes openings formed between fibersthereof.

38. The medical device of any one of paragraphs 33 through 37, whereinthe substrate is nonwoven.

39. The medical device of any one of paragraphs 33 through 38, whereinthe filler material is selected from the group consisting ofuncrosslinked molecules, hydrogels, absorbable polymer spheres,interpenetrating chemically or ionically crosslinked hydrogels, andcombinations thereof.

While the above description contains many specifics, these specificsshould not be construed as limitations on the scope of the presentdisclosure, but merely as exemplifications of embodiments thereof. It isenvisioned that the elements and features illustrated or described inconnection with one exemplary embodiment may be combined with theelements and features of another exemplary embodiment without departingfrom the scope of the present disclosure, and that such modificationsand variations are also intended to be included within the scope of thepresent disclosure. Those skilled in the art will envision many otherpossible variations that are within the scope and spirit of the presentdisclosure.

What is claimed is:
 1. A method of making an absorbent surgicalbuttress, comprising: generating a plurality of fibers; collecting theplurality of fibers so that they adhere to one another and form anon-woven material; plasma treating at least a portion of a surface ofthe non-woven material with an ionizable gas species or combination ofionizable gas species configured to chemically modify or functionalizethe surface of the non-woven material; and cutting the non-wovenmaterial into a desired shape for a surgical buttress.
 2. The method ofmaking an absorbent surgical buttress according to claim 1, wherein theionizable gas species is selected from the group consisting of air,water vapor, oxygen, nitrogen, argon, and combinations thereof.
 3. Themethod of making an absorbent surgical buttress according to claim 1,wherein the fibers are melt extruded.
 4. The method of making anabsorbent surgical buttress according to claim 3, further comprisingblowing hot air at the fibers as they exit a die head and before theyare collected.
 5. The method of making an absorbent surgical buttressaccording to claim 3, further comprising blowing hot air at the fibersas they exit the die head and before they are collected, the hot airhaving a temperature greater than or equal to the melting temperature ofthe fibers.
 6. The method of making an absorbent surgical buttressaccording to claim 4, wherein the fibers are collected as they cool. 7.The method of making an absorbent surgical buttress according to claim1, wherein the fibers are melt extruded from a polymer selected from thegroup consisting of lactide homopolymer, glycolide homopolymer,polydioxanone homopolymer, glycolide trimethylene carbonate copolymer,glycolide lactide copolymer, glycolide dioxanone trimethylene carbonatecopolymer, and glycolide caprolactone trimethylene carbonate lactidecopolymer.
 8. The method of making an absorbent surgical buttressaccording to claim 1, wherein the fibers are made from a bioabsorbablepolymeric material.
 9. The method of making an absorbent surgicalbuttress according to claim 3, wherein the melting temperature of thepolymer is between about 180 and about 250 degrees celcius.
 10. Themethod of making an absorbent surgical buttress according to claim 3,wherein the melting temperature of the polymer is between about 80degrees celcius and about 190 degrees celsius.
 11. The method of makingan absorbent surgical buttress according to claim 4, wherein the hot airhas a temperature of between about 270 and about 290 degrees celcius.12. The method of making an absorbent surgical buttress according toclaim 1, wherein the fibers are collected on a conveyor surface.
 13. Themethod of making an absorbent surgical buttress according to claim 1,further comprising applying heat and pressure to the non-woven materialbefore plasma treating the non-woven material.
 14. The method of makingan absorbent surgical buttress according to claim 1, wherein thenon-woven material is cut into a shape corresponding to the shape of alinear surgical stapler.
 15. The method of making an absorbent surgicalbuttress according to claim 1, wherein the non-woven material is cutinto a shape corresponding to the shape of a circular surgical stapler.16. The method of making an absorbent surgical buttress according toclaim 4, wherein the fibers are generated by melt extruding a copolymerof glycolide, caprolactone, trimethylene carbonate and lactide having amelting temperature between about 140 degrees celcius and about 185degrees celcius.
 17. The method of making an absorbent surgical buttressaccording to claim 16, wherein the hot air blown at the fibers has atemperature between about 185 degrees celcius and about 195 degreescelcius.
 18. The method of making an absorbent surgical buttressaccording to claim 4, wherein the fibers are generated by melt extrudingdioxanone having a melting temperature between about 80 degrees celciusand about 125 degrees celsius.
 19. The method of making an absorbentsurgical buttress according to claim 18, wherein the air blown at thedioxanone fibers has a temperature between about 145 degrees celcius andabout 155 degrees celcius
 20. An absorbent surgical buttress, comprisinga non-woven material having a plurality of fibers adhered to oneanother, the fibers being formed from a melt extruded bioabsorbablepolymeric material, the non-woven material being plasma treated on atleast a portion of a surface of the non-woven material so that thesurface is chemically modified or functionalized, the non-woven materialbeing cut into a desired shape for the surgical buttress.
 21. Theabsorbent surgical buttress according to claim 20, wherein the fibersare formed from a polymeric material selected from the group consistingof lactide homopolymer, glycolide homopolymer, polydioxanonehomopolymer, glycolide trimethylene carbonate copolymer, glycolidelactide copolymer, glycolide dioxanone trimethylene carbonate, andglycolide caprolactone trimethylene carbonate lactide.
 22. The absorbentsurgical buttress according to claim 20, wherein the fibers are formedfrom a polymeric material having a melting temperature of between about180 and 250 degrees celcius.
 23. The absorbent surgical buttressaccording to claim 20, wherein the fibers are formed from a polymericmaterial having a melting temperature of between about 80 degreescelcius and about 190 degrees celcius.
 24. The absorbent surgicalbuttress according to claim 20, wherein the non-woven material is cutinto a shape corresponding to the shape of a linear surgical stapler.25. The absorbent surgical buttress according to claim 20, wherein thenon-woven material is cut into a shape corresponding to the shape of acircular surgical stapler.